4-tert-Butylcalix[4]arenes containing azacrown ether substituents at the narrow rim as membrane carriers

Article abstract of DOI:10.1007/s11172-015-0953-z

Calixarenes substituted at the narrow rim with one or four N-methoxycarbonylmonoaza12-crown-4 moieties were used in liquid membranes to transport transition metal chlorides.

Full text of DOI:10.1007/s11172-015-0953-z

Russian Chemical Bulletin, International Edition, Vol. 64, No. 4, pp. 905—908, April, 2015
905
4ꢀtertꢀButylcalix[4]arenes containing azacrown ether substituents
at the narrow rim as membrane carriers
E. A. Ivanova,a P. E. Prokhorova,a Yu. Yu. Morzherin,a A. P. Lukyanenko,a,b E. A. Alekseeva,b and S. S. Basokb
aUral Federal University,
19 ul. Mira, 620002 Ekaterinburg, Russian Federation.
Eꢀmail: yu.yu.morzherin@urfu.ru
bA. V. Bogatskii Physicochemical Institute of the National Academy of Sciences of the Ukraine,
86 ul. Lyustdorfskaya doroga, 65080 Odessa, Ukraine.
Fax: +38 (048) 765 9602
Calixarenes substituted at the narrow rim with one or four Nꢀmethoxycarbonylmonoazaꢀ
12ꢀcrownꢀ4 moieties were used in liquid membranes to transport transition metal chlorides.
Key words: calixarenes, liquid membranes, metal ion transport.
Together with crown ethers,1,2 cryptands,2,3 and cycloꢀ
dextrines,4,5 calixarenes6—8 are a large class of supraꢀ
molecular hosts, which can recognize cations,9—11 anꢀ
ions,12—14 and neutral molecules,15 as well as are used for
the energetic transport.16
The transport of molecules or ions which uses liquid
membranes is very promising as an approach to the selecꢀ
tive separation, since in liquid membranes, in contrast to
the solid, one can use carrier molecules, that considerably
increases selectivity of the membranes. In particular, liquid
membranes were used to extract heavy metals from indusꢀ
trial waste water.17—19
The selectivity can be significantly increased by the
introduction in the liquid membrane of carrier moleꢀ
cules having an affinity to any component in the source
phase. The carrier accelerates the transport of this specifꢀ
ic component.20 Usually, crown ether derivatives are used
as carrier molecules. Calixarenes are also promising
substrates for the use in liquid membranes.21 We beꢀ
lieve that the introduction of several azaꢀ12ꢀcrownꢀ4
moieties into a preorganized structure of calix[4]arene
in the cone conformation will make it possible to design
a selective receptor for transition metal ions. Since the
calixarene core is a relatively rigid framework, and crown
ethers are attached to it by a short linker, one should exꢀ
pect that the sandwich or pseudosandwich type of comꢀ
plexes will be formed with the metal cations with large
ionic radius.
The purpose of the present work is to study the transꢀ
port of transition metal cations through a liquid memꢀ
brane, using calixarene derivatives 1—3 modified at the
narrow rim with one, two, or four carbonylazacrown ether
moieties as carrier molecules. Calixarene crown ethers 1
and 3 were obtained similarly to calixarene 2 (see Ref. 22
and 23) by the alkaline hydrolysis from tetra and mono
esters of calix[4]arene derivatives 4 and 5 with subsequent
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0905—0908, April, 2015.
1066ꢀ5285/15/6404ꢀ0905 © 2015 Springer Science+Business Media, Inc.

906
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
Ivanova et al.
Scheme 1
Reagents: i. 1) NaOH, 2) HCl; ii. 1ꢀazaꢀ12ꢀcrownꢀ4, DCC.
amidation of the corresponding carboxylic acids 6 and 7
by carbodiimide method (Scheme 1).
chlorides through the membrane and considerably increasꢀ
es the flow of cobalt (72ꢀfold) and nickel (17ꢀfold) chloꢀ
rides. It should be noted that the introduction of azacrown
We studied the transport of salts CoCl2, NiCl2, CuCl2,
and MgCl2 through the liquid membrane impregnated with
calixarenes 1—5. A typical pattern of the increase in the
concentration of the salt in the receiving phase is shown in
Fig. 1. In control experiments, the substrates under study
were transported through the membrane containing no
carrier. Based on the data obtained, an increase in the flow
through the membrane containing a carrier molecule in
comparison with the control experiment was determined
for each salt. The data are given in Table 1.
As compared to the control experiment, calixarene 3
increases the transport rate of nickel and magnesium chloꢀ
rides threeꢀfold, of cobalt chloride twoꢀfold, but does not
affect the transport of copper chloride. Compound 1 inꢀ
creases twoꢀfold the flow rate of copper and magnesium
C/mol L–1
0.5
0.4
0.3
0.2
0.1
5000
10000
15000
20000
t/s
Fig. 1. Increases in the concentration of CoCl2 (C) in the receivꢀ
ing phase with time (t).
Table 1. The values of initial flow (mol s–1 m–2) of salts through the liquid membrane impregnated
with calix[4]arenes 1—5 at 20 C
Salt
1
2
3
4
5
Control
CoCl2
NiCl2
CuCl2
MgCl2
5.38•10–4
6.87•10–5
1.40•10–5
1.58•10–5
5.17•10–4
6.45•10–5
1.57•10–5
1.55•10–5
1.69•10–5
1.29•10–5
6.50•10–6
2.24•10–5
2.62•10–5
2.15•10–5
1.34•10–5
1.50•10–5
8.32•10–6
5.30•10–6
7.34•10–6
1.36•10–5
7.50•10–6
4.14•10–6
6.38•10–6
7.20•10–6
* The experimental error is less than 5% at a 95% confidence interval.

Azacrown calixarenes as membrane carriers
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
907
was a solution of the carrier (0.02 mmol) in oꢀnitrophenyl octyl
ether (0.02 mL) impregnated into the pores of polytetrafluoroꢀ
ethylene membranes (SigmaꢀAldrich, diameter 25 mm, pore sizes
0.2 m). The appliance was similar to that described in the
work.28 The source phase was a 1 M solution of the salt. The
concentration of the substrate in the receiving phase (distilled
water, V = 400 mL) was determined measuring the conductivity
of the solution.
ether moieties into the structure of ligands 1—3 instead of
tetra ester derivatives 4 also increases the flow of cobalt
and nickel chlorides, however, only an insignificant inꢀ
crease in the flow is observed for copper and magnesium
chlorides. The use of the disubstituted calix[4]arene 2 as
a carrier gave the results similar to those obtained for tetraꢀ
substituted calixarene 1, hence, a possible formation of
the sandwich complex can be suggested.
This work was financially supported by the Ministry of
Education and Science of the Russian Federation (State
Assignment No. 4.560.2014ꢀK).
In conclusion, we showed that calixarenes substituted
at the lower rim with the Nꢀmethoxycarbonylmonoazaꢀ
12ꢀcrownꢀ4 ether fragments can be used for the memꢀ
brane transport, with diꢀ and tetrasubstituted calix[4]ꢀ
arenes being the most efficient for the transport of cobalt
and nickel chlorides.
References
1. X. Ji, J. Li, J. Chen, X. Chi, K. Zhu, X. Yan, M. Zhang,
F. Huang, Macromolecules, 2012, 45, 6457.
2. M. Zhang, K. Zhu, F. Huang, Chem. Commun., 2010,
46, 8131.
3. S. Ok Kang, J. M. Llinares, V. W. Dayc, K. BowmanꢀJames,
Chem. Soc. Rev., 2010, 39, 3980.
4. B. V. K. J. Schmidt, M. Hetzer, H. Ritter, C. BarnerꢀKoꢀ
wollik, Prog. Polym. Sci., 2014, 39, 235.
5. N. Zafar, H. Fessi, A. Elaissari, Int. J. Pharmaceut., 2014,
461, 351.
Experimental
Reaction progress and individuality of synthesized comꢀ
pounds were monitored by thinꢀlayer chromatography on Silufol
UVꢀ254 plates in the systems chloroform, chloroform—ethanol
(9 : 1), ethyl acetate—hexane (1 : 1), (1 : 2), (1 : 5). 1H NMR
spectra were recorded on a spectrophotometer Bruker DRXꢀ400
(400 MHz) with Me4Si as an internal standard. Elemental analꢀ
ysis was performed on a PE 2400 Series II CHNSꢀanalyzer.
Mass spectra were recorded on a Varian MAT 311A spectroꢀ
meter (electron impact) at 70 eV of ionizing voltage with direct
injection of samples into the source of ions. Conductivity of
solutions was measured on a Radelkis OKꢀ102 conductometer.
Solvents were purified according to the standard procedures.
Melting points were not corrected.
Compounds 2,22,23 4,24,25 5,26 6,24 and 727 were synthesized
according to the described procedures.
5,11,17,23ꢀTetraꢀtertꢀbutylꢀ25,26,2728ꢀtetra((1,4,7ꢀtriꢀ
oxaꢀ10ꢀazacyclodecꢀ10ꢀyl)carbonylmethoxy)calix[4]arene (1)
was obtained similarly to calixarene 2. The yield was 95%. B.p.
6. T. Nabeshima, S. Akine, Chem. Rec., 2008, 8, 240.
7. M. A. Qazi, I. Qureshi, S. Memon, J. Fluoresc., 2011, 21, 1231.
~
8. N. Basílio, Á. Pineiro, J. P. Da Silva, L. GarcíaꢀRío, J. Org.
Chem., 2013, 78, 9113.
9. B. Tabakci, O. Alici, I. Karatas, Talanta, 2013, 106, 92.
10. A. A. Abramov, A. N. Vasiliev, O. V. Dubovaya, V. V. Kovaꢀ
lev, I. M. Vatsouro, Mendeleev Commun., 2012, 22, 260.
11. Y. Yang, X. Cao, D. W. Purkiss, J. F. Cannon, R. A. Bartsch,
Tetrahedron, 2012, 68, 2233.
12. N. Y. Edwards, A. L. Possanza, Supramol. Chem., 2013,
25, 446.
13. N. Y. Edwards, F. Liub, G. Chen, Supramol. Chem., 2013,
25, 631.
14. S. Licen, V. Bagnacani, L. Baldini, A. Casnati, F. Sansone,
M. Giannetto, P. Pengo, P. Tecilla, Supramol. Chem., 2013,
25, 481.
15. P. Curínová, M. Pojarová, J. Budka, K. Lang, I. Stibor,
P. Lhoták, Tetrahedron, 2010, 66, 8047.
16. B. S. Creaven, D. F. Donlon, J. McGinley, Coord. Chem.
Rev., 2009, 253, 893.
17. R. Ludwig, K. Kunogi, N. Dung, S. Tachimori, Chem. Comꢀ
mun., 1997, 1985.
18. J. S. Kim, S. K. Kim, J. W. Ko, E. T. Kim, S. H. Yu,
M. H. Cho, S. G. Kwon, E. H. Lee, Talanta, 2000, 52, 1143.
19. M. Sugiura, Sep. Sci. Techol., 1990, 25, 1189.
20. M. Mulder, Basic Prinsiples of Membrane Technology, 2nd ed.,
Kluwer Acad. Publ., Derdrecht—Boston—London, 1996,
564 pp.
21. B. Mokhtari, K. Pourabdollah, J. Chin. Chem. Soc., 2012,
59, 1058.
22. E. A. Alekseeva, S. S. Basok, I. M. Rakipov, A. V. Mazepa,
A. I. Gren´, Russ. J. Org. Chem. (Engl. Transl.), 2013, 49,
1035 [Zh. Org. Khim., 2013, 49, 1050].
1
278—280 C. H NMR (CDCl3), : 6.97 (s, 8 H, 8 ArH); 5.02,
3.39 (both d, 8 H, 4 ArCH2Ar, J = 13.8 Hz); 4.81 (s, 8 H,
4 OCH2C=O); 4.00 (br.t, 8 H, OCH2, J = 4.8 Hz); 3.80 (br.t,
8 H, OCH2, J = 4.5 Hz); 3.66 (br.t, 8 H, OCH2, J = 4.8 Hz);
3.55—3.64 (m, 40 H, OCH2, NCH2); 1.21 (s, 36 H, 4 (CH3)3C).
MS (EI, 70 eV), m/z (Irel (%)): 1511 (12), 1510 (27), 1509 (30)
[M]+. Found (%): C, 66.47; H, 8.32; N, 3.65. C84H124N4O20
Calculated (%): C, 66.82; H, 8.28; N, 3.71.
5,11,17,23ꢀTetraꢀtertꢀbutylꢀ25ꢀ(1,4,7ꢀtrioxaꢀ10ꢀazacycloꢀ
decꢀ10ꢀyl)carbonylmethoxyꢀ26,27,28ꢀtrihydroxycalix[4]arene
(3) was obtained similarly to calixarene 2. The yield was 92%.
B.p. 295—297 C. 1H NMR (CDCl3), : 10.25 (s, 1 H, OH); 9.33
(s, 2 H, OH); 7.11 (s, 2 H, ArH); 7.08 (s, 4 H, ArH); 7.00 (s, 2 H,
ArH); 4.90 (s, 2 H, OCH2C=O); 4.50 (d, 2 H, ArCH2Ar,
J = 13.8 Hz); 4.31 (d, 2 H, ArCH2Ar, J = 13.8 Hz); 4.02 (br.t, 2 H,
OCH2, J = 4.8 Hz); 3.80 (br.t, 2 H, OCH2, J = 4.8 Hz); 3.67
(br.t, 2 H, OCH2, J = 4.7 Hz); 3.55—3.64 (m, 10 H, OCH2,
NCH2); 1.25 (s, 9 H, (CH3)3C); 1.22 (s, 18 H, (CH3)3C); 1.05
(s, 9 H, (CH3)3C). MS (EI, 70 eV), m/z (Irel (%)): 865 (50), 864
(85) [M]+. Found (%): C, 74.77; H, 8.75; N, 1.65. C54H73NO8.
Calculated (%): C, 75.05; H, 8.51; N, 1.62.
.
Studies of transport through a liquid membrane. The flow
through the liquid impregnated membranes was measured in
a glass vessel, using a platinum electrode. The liquid membrane
23. E. A. Alekseeva, S. S. Basok, A. V. Mazepa, A. P. Luk´yaꢀ
nenko, O. V. Snurnikova, A. I. Gren´, Russ. J. Gen. Chem.

908
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
Ivanova et al.
(Engl. Transl.), 2013, 83, 1738 [Zh. Obshch. Khim., 2013,
83, 1519].
27. C. Gaeta, M. De Rosa, M. Fruilo, A. Soriente, P. Neri,
Tetrahedron: Asymmetry, 2005, 16, 2333.
24. S.ꢀK. Chang, I. Cho, J. Chem. Soc., Perkin Trans. 1,
1986, 211.
25. J. A. J. Brunink, W. Verboom, J. F. J. Engbersen, S. Harkeꢀ
ma, D. N. Reinhoudt, Rec. Trav. Chim. PaysꢀBas, 1992,
111, 511.
28. I. S. Antipin, I. I. Stoikov, A. A. Khrustalev, A. I. Konovꢀ
alov, Russ. Chem. Bull. (Int. Ed.), 2001, 50, 2134 [Izv. Akad.
Nauk, Ser. Khim., 2001, 2038].
26. L. C. Groenen, B. H. M. Ruël, A. Casnati, W. Verboom,
A. Pochini, R. Ungaro, D. N. Reinhoudt, Tetrahedron, 1991,
47, 8379.
Received April 30, 2014;
in revised form September 30, 2014